U.S. patent number 4,395,370 [Application Number 06/329,222] was granted by the patent office on 1983-07-26 for branched chain alkenyl methyl carbonates, uses thereof in augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles and formate intermediates useful in preparing same.
This patent grant is currently assigned to International Flavors & Fragrances Inc.. Invention is credited to Richard M. Boden, Michael Licciardello, Theodore J. Tyszkiewicz.
United States Patent |
4,395,370 |
Boden , et al. |
July 26, 1983 |
Branched chain alkenyl methyl carbonates, uses thereof in
augmenting or enhancing the aroma of perfume compositions, colognes
and perfumed articles and formate intermediates useful in preparing
same
Abstract
Described are branched chain alkenyl methyl carbonates and
branched chain alkenyl formates defined according to the structure:
##STR1## wherein R.sub.3 represents hydrogen or methoxy and wherein
in each of the molecules described by the structure, one of the
dashed lines is a carbon-carbon double bond and each of the other
of the dashed lines is a carbon-carbon single bond; and uses of the
compounds wherein R.sub.3 is methoxy in augmenting or enhancing the
aroma of perfume compositions, colognes and perfumed articles such
as solid or liquid anionic, cationic, nonionic or zwitterionic
detergents, fabric softener compositions, fabric softener articles,
hair sprays, shampoos, bath oils and plastic fragrances.
Inventors: |
Boden; Richard M. (Monmouth
Beach, NJ), Tyszkiewicz; Theodore J. (Sayreville, NJ),
Licciardello; Michael (Farmingdale, NJ) |
Assignee: |
International Flavors &
Fragrances Inc. (New York, NY)
|
Family
ID: |
23284414 |
Appl.
No.: |
06/329,222 |
Filed: |
December 10, 1981 |
Current U.S.
Class: |
558/260; 424/69;
510/101; 512/26; 560/261 |
Current CPC
Class: |
C07C
45/46 (20130101); C11B 9/0015 (20130101); C07C
67/08 (20130101); C07C 69/96 (20130101); C07C
67/02 (20130101); C07C 45/46 (20130101); C07C
49/203 (20130101); C07C 67/08 (20130101); C07C
69/07 (20130101); C07C 67/02 (20130101); C07C
69/96 (20130101) |
Current International
Class: |
C07C
45/00 (20060101); C07C 45/46 (20060101); C11B
9/00 (20060101); C07C 069/96 (); A61K 007/46 () |
Field of
Search: |
;260/463 ;560/261 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Chemical Abstracts, Seventh Collective Index, 1962-66, Subjects
Bf-Cho, "Carbonic Acid"..
|
Primary Examiner: Daus; Donald G.
Assistant Examiner: Eakin; M. C.
Attorney, Agent or Firm: Liberman; Arthur L.
Claims
What is claimed is:
1. An ester defined according to the structure: ##STR69## wherein
one of the dashed lines represents a carbon-carbon double bond and
each of the other of the dashed lines represent carbon-carbon
single bonds.
2. A mixture produced according to the process of:
(a) dimerizing isoamylene in order to form a mixture of
diisoamylene isomers defined according to the structure: ##STR70##
wherein R.sub.1 ", R.sub.2 ", R.sub.3 ", R.sub.4 " and R.sub.5 "
represent hydrogen or methyl with three of R.sub.1 ", R.sub.2 ",
R.sub.3 ", R.sub.4 " and R.sub.5 " representing methyl and the
other two of R.sub.1 ", R.sub.2 ", R.sub.3 ", R.sub.4 " and R.sub.5
" representing hydrogen;
(b) acetylating the resulting diisoamylene derivative with acetic
anhydride or an acetyl halide in order to form a mixture of
compounds defined according to the structure: ##STR71## (c)
reducing the resulting compound in order to form a mixture of
carbinols defined according to the structure: ##STR72## (d)
reacting the resulting carbinol with formic acid in order to form a
formate defined according to the structure: ##STR73## (e) reacting
the resulting formate with dimethyl carbonate in order to form the
compounds defined according to the structure: ##STR74##
Description
BACKGROUND OF THE INVENTION
The instant invention provides novel, branched chain alkenyl
carbonates and formate intermediate for producing same defined
according to the generic structure: ##STR2## wherein R.sub.3
represents hydrogen or methoxy and wherein in each of the molecules
defined by the structure, one of the dashed lines represents a
carbon-carbon double bond and each of the other of the dashed lines
represent carbon-carbon single bonds, and in the compounds wherein
R.sub.3 is methoxy, uses thereof in augmenting or enhancing the
aroma of consumable materials.
Materials which can provide myrrh-like and labdanum-like aroma
nuances are well known in the art of perfumery. Many of the natural
substances which provide such fragrances and contribute the desired
nuances to perfumery compositions are high in cost, vary in quality
from one batch to another and/or are generally subject to the usual
variations of natural products.
The prior art contains a large number of teachings regarding the
use of organic carbonates in augmenting or enhancing the aroma of
perfumes. Thus, U.S. Pat. No. 4,033,993 discloses the use of
organic carbonates defined according to the structure: ##STR3##
wherein R.sub.1 is a moiety having from 8 to 12 carbon atoms
selected from the group consisting of alkylcyclohexyl,
alkenylcyclohexyl, alkynylcyclohexyl and cycloalkyl and R.sub.2 is
a moiety selected from the group consisting of alkyl having from 1
to 5 carbon atoms, alkenyl having from 2 to 5 carbon atoms and
alkynyl having from 2 to 5 carbon atoms. U.S. Pat. No. 4,033,993
describes, for example, methyl-1-ethynycyclohexyl carbonate having
a fruity, herbal complex odor and distinct fragrance of dill. In
addition, U.S. Pat. No. 4,033,993 describes methyl cyclooctyl
carbonate as having an herbal, natural and complex fragrance which
is distinguished by a strong and long clinging flowery jasmine
scent and further indicates its use in jasmine perfume
compositions. U.S. Pat No. 4,033,993 describes the preparation of
the compounds defined according to the structure: ##STR4##
according to the reaction: ##STR5## where R.sub.1 and R.sub.2 are
defined as above.
In addition, U.S. Pat. No. 4,080,309 describes the perfume use of
the carbonates defined according to the structure: ##STR6## wherein
R.sub.1 ' is a moiety having from 8 to 12 carbon atoms selected
from the group consisting of alkylcyclohexyl, alkenylcyclohexyl,
alkynylcyclohexyl and cycloalkyl and R.sub.2 ' is a moiety selected
from the group consisting of alkyl having from 1 to 5 carbon atoms,
alkenyl having from 2 to 5 carbon atoms and alkynyl having from 2
to 5 carbon atoms. Described in U.S. Pat. No. 4,080,309 are also
such compounds as methyl cyclooctyl carbonate and the use thereof
in jasmine perfume formulations. As is the case in U.S. Pat. No.
4,033,993, the carbonates of U.S. Pat. No. 4,080,309 are indicated
to be prepared according to the reaction: ##STR7##
Nothing in the prior art, however, discloses the branched chain
alkenyl methyl carbonates having the specific fragrance nuances of
our invention and nothing in the prior art discloses the branched
chain alkenyl formates which are useful as intermediates for
preparing such carbonates.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. AA represents the GLC profile for the reaction product of
Example A using a 70% sulfuric acid catalyst at 35.degree. C.
FIG. AB represents the GLC profile for the reaction product of
Example A using an Amberlyst.RTM. 15 acidic ion exchange resin
catalyst at a temperature of 150.degree. C.
FIG. AC represents the GLC profile for the reaction product of
Example A using an Amberlyst.RTM. 15 catalyst at 100.degree. C.
FIG. AD represents the GLC profile for the reaction product of
Example A using a sulfuric acid catalyst and an alpha-methyl
styrene diluent at 35.degree. C. according to the conditions of
United Kingdom Patent Specification No. 796,130 (crude reaction
product).
FIG. AE represents the GLC profile for the reaction product of
Example A using a sulfuric acid catalyst at 35.degree. C. and an
alpha-methyl styrene diluent according to the conditions of United
Kingdom Patent Specification No. 796,130 (distilled reaction
product). Distillation range: 36.degree.-40.degree. C. vapor
temperature; 74.degree.-94.degree. C. liquid temperature and 4-5
mm/Hg pressure.
FIG. BA represents the NMR spectrum for peak 301 of the GLC profile
of FIG. AE. Peak 301 has been determined by analysis to be the
compound having the structure: ##STR8##
FIG. BB represents the infra-red spectrum for peak 301 of the GLC
profile of FIG. AE.
FIG. CA represents the NMR spectrum for peak 302 of the GLC profile
of FIG. AE. Peak 302 contains the compounds having the structures:
##STR9##
FIG. CB represents the infra-red spectrum for peak 302 of the GLC
profile of FIG. AE.
FIG. D represents the NMR spectrum for peak 302 of the GLC profile
of FIG. AB.
FIG. 1 set forth the GLC profile for the reaction product of
Example I, containing compounds defined according to the structure:
##STR10## wherein in each molecule of the mixture, one of the
dashed lines is a carbon-carbon double bond and the other of the
dashed lines are carbon-carbon single bonds.
FIG. 2A represents the infra-red spectrum of Peak 3 of the GLC
profile of FIG. 1.
FIG. 2B represents the infra-red spectrum of Peak 4 of the GLC
profile of FIG. 1.
FIG. 2C represents the infra-red spectrum for Peak 5 of the GLC
profile of FIG. 1.
FIG. 2D represents the infra-red spectrum for Peak 6 of the GLC
profile of FIG. 1.
FIG. 2E represents the infra-red spectrum for Peak 7 of the GLC
profile of FIG. 1.
FIG. 2F represents the infra-red spectrum for Peak 8 of the GLC
profile of FIG. 1.
FIG. 2G represents the infra-red spectrum for Peak 9 of the GLC
profile of FIG. 1.
FIG. 2H represents the infra-red spectrum for Peak 10 of the GLC
profile of FIG. 1.
FIG. 2J represents the NMR spectrum for a mixture of compounds
having the structures: ##STR11## produced according to Example
I.
FIG. 2K represents the NMR spectrum for the compound having the
structure: ##STR12## produced according to Example I.
FIG. 2L represents the NMR spectrum for the compound containing the
structure: ##STR13## produced according to Example I.
FIG. 3 represents the GLC profile for the reaction product of
Example II(A) containing structures defined according to the genus
having the structure: ##STR14## wherein in each of the molecules of
the mixture, one of the dashed lines represents a carbon-carbon
double bond and each of the other of the dashed lines represent
carbon-carbon single bonds.
FIG. 4 represents the GLC profile for the reaction product of
Example II(B) containing a mixture of compounds defined according
to the structure: ##STR15## wherein in each of the molecules of the
mixture, one of the dashed lines represents a carbon-carbon double
bond and each of the other of the dashed lines represent
carbon-carbon single bonds.
FIG. 5 is the GLC profile for the reaction product mixture prepared
according to Example III (conditions: SF 96 column, 6'.times.1/4";
programmed at 100.degree.-220.degree. C. at 8.degree. C. per
minute).
FIG. 6 is the infra-red spectrum for the reaction product mixture
prepared according to Example III containing compounds defined
according to the structure: ##STR16## wherein in each of the
molecules of the mixture, one of the dashed lines represents a
carbon-carbon double bond and each of the other of the dashed lines
represents carbon-carbon single bonds.
FIG. 7 is the GLC profile for the reaction product of Example
IV(A), the formate ester mixture, containing compounds defined
according to the structure: ##STR17## wherein in each of the
molecules of the mixture, one of the dashed lines represents a
carbon-carbon double bond and each of the other of the dashed lines
represent carbon-carbon single bonds (conditions: 12% SF 96 column,
6'.times.1/4", programmed at 100.degree.-220.degree. C. at
8.degree. C. per minute).
FIG. 8 is the GLC profile for the distillation product (fraction 5)
of the reaction product of Example IV(B) containing a mixture of
compounds defined according to the structure: ##STR18## wherein in
the mixture, in each of the molecules one of the dashed lines
represents a carbon-carbon double bond and each of the other of the
dashed lines represent carbon-carbon single bonds (conditions: 12%
SF 96 column, 6'.times.1/4" programmed at 100.degree.-220.degree.
C. at 8.degree. C. per minute).
FIG. 9 is the NMR spectrum for fraction 5 of the distillation
product of the reaction product of Example IV(B) containing a
mixture of compounds defined according to the structure: ##STR19##
wherein in the mixture, in each of the molecules one of the dashed
lines represents a carbon-carbon double bond and each of the other
of the dashed lines represent carbon-carbon single bonds.
FIG. 10 is the infra-red spectrum for fraction 5 of the
distillation product of the reaction product of Example IV(B)
containing a mixture of compounds defined according to the
structure: ##STR20## wherein in the mixture, in each of the
molecules one of the dashed lines represents a carbon-carbon double
bond and each of the other of the dashed lines represent
carbon-carbon single bonds.
DETAILED DESCRIPTION OF THE DRAWINGS
FIG. AE represents the GLC profile for the reaction product of
Example A wherein a sulfuric acid catalyst catalyzes the
dimerization of isoamylene to form diisoamylene in the presence of
an alpha-methyl styrene diluent according to the conditions of
United Kingdom Patent Specification No. 796,130. Peak 301 has been
determined by analysis to be the compound having the structure:
##STR21## Peak 302 of the GLC profile contains the compounds having
the structures: ##STR22##
DISCLOSURES INCORPORATED BY REFERENCE HEREIN
The following applications for United States Letters Patent are
incorporated by reference herein:
(a) U.S. Application for Letters Patent Ser. No. 160,788 filed on
June 19, 1980 now U.S. Pat. No. 4,287,084 issued on Sept. 1, 1981
(entitled: "USE OF MIXTURE OF ALIPHATIC C.sub.10 BRANCHED OLEFINS
IN AUGMENTING OR ENHANCING THE AROMA OF PERFUMES AND/OR PERFUMED
ARTICLES") setting forth the use of the compounds having the
structures: ##STR23## or generically, the compounds defined
according to the structure: ##STR24## wherein R.sub.1 ", R.sub.2 ",
R.sub.3 ", R.sub.4 " and R.sub.5 " represent hydrogen or methyl
with three of R.sub.1 ", R.sub.2 ", R.sub.3 ", R.sub.4 " and
R.sub.5 " representing methyl and the other two of R.sub.1 ",
R.sub.2 ", R.sub.3 ", R.sub.4 " and R.sub.5 " representing
hydrogen;
(b) Application for U.S. Letters Patent Ser. No. 188,576 filed on
Sept. 18, 1980, now U.S. Pat. No. 4,303,555 issued on Dec. 1, 1981
a continuation-in-part of Ser. No. 160,788 filed on June 19, 1980;
now U.S. Pat. No. 4,287,084 issued on Sept. 1, 1981
and
Application for U.S. Letters Patent Ser. No. 184,132 filed on Sept.
4, 1980, now U.S. Pat. No. 4,321,255 issued on Mar. 23, 1982
entitled "BRANCHED KETONES; ORGANOLEPTIC USES THEREOF AND PROCESS
FOR PREPARING SAME" disclosing the reaction: ##STR25## wherein
R.sub.1 ', R.sub.2 ' and R.sub.3 ' represent C.sub.1 -C.sub.3 lower
alkyl and R.sub.4 ' is either of R.sub.1 ', R.sub.2 ' and R.sub.3 '
and wherein X' is chloro or bromo, and the use of the resulting
compounds for their organoleptic properties.
(d) Application for U.S. Letters Patent Ser. No. 252,334 filed on
Apr. 9, 1981 now U.S. Pat. No. 4,336,164 issued on June 22, 1982 is
directed to the use of the compounds defined according to the
generic structure: ##STR26## as starting materials wherein R.sub.4
' is C.sub.1 -C.sub.3 lower alkyl and wherein one of the dashed
lines represents a carbon-carbon double bond and each of the other
of the dashed lines represent carbon-carbon single bonds produced
according to the process of Application for United States Letters
Patent Ser. No. 184,132 filed on Sept. 4, 1980 now U.S. Pat. No.
4,321,255 issued on Mar. 23, 1982 entitled: "BRANCHED KETONES,
ORGANOLEPTIC USES THEREOF AND PROCESS FOR PREPARING SAME".
(e) Application for U.S. Letters Patent Ser. No. 252,334 filed on
Apr. 9, 1981, now U.S. Pat. No. 4,336,164 issued on June 22, 1982
discloses the use of certain branched chain olefinic secondary
alcohols having the generic structure: ##STR27## wherein R.sub.1
represents methyl or isopropyl, which compounds are capable of
imparting a variety of flavors and fragrances to various consumable
materials. In this compound, one of the dashed lines represents a
carbon-carbon double bond and each of the other of the dashed lines
represent carbon-carbon single bonds.
THE INVENTION
The present invention provides compounds defined according to the
structure: ##STR28## wherein R.sub.3 represents hydrogen or methoxy
and wherein one of the dashed lines represents a carbon-carbon
double bond and each of the other of the dashed lines represent
carbon-carbon single bonds. The present invention also provides an
economical, efficient process for synthesizing the compound having
the structure: ##STR29## by reacting dimethyl carbonate with the
formate ester of diisoamylene methyl carbinol in the presence of an
alkali metal alkoxide according to the reaction: ##STR30##
The present invention also provides processes for using the
compounds defined according to the generic structure: ##STR31##
wherein one of the dashed lines represents a carbon-carbon double
bond and each of the other of the dashed lines represent
carbon-carbon single bonds for their organoleptic properties in
augmenting or enhancing the organoleptic properties of consumable
materials, that is, the aroma of perfumes, colognes, and perfumed
articles (such as perfumed polymers, solid or liquid cationic,
anionic, nonionic or zwitterionic detergents, soaps, fabric
softener compositions, fabric softener articles including
drier-added fabric softener articles such as BOUNCE.RTM.
(registered trademark of the Procter & Gamble Company of
Cincinnati, Ohio), fabric brighteners, cosmetic powders, bath
preparations, hair preparations such as hair sprays and
shampoos).
The branched chain alkenyl carbonates of our invention are either
usable in admixture with one another, or the isomers are usable in
admixture with one another such as mixtures of compounds defined
according to the structure: ##STR32## wherein one of the dashed
lines in each of the molecules of the mixture represents a
carbon-carbon double bond and each of the other of the dashed lines
in each of the molecules of the mixture represent carbon-carbon
single bonds, or they may be used as individual compounds which
are, for example, defined according to the structures such as:
##STR33## wherein R.sub.3 is methoxy and wherein the compound
having the structure: ##STR34## differs from the compound having
the structure: ##STR35## one of the structures being "cis" with
respect to the methyl groups on the carbon atoms which make up the
carbon-carbon double bond and the other of the structures being
"trans" with respect to the methyl groups on the carbon atoms which
make up the carbon-carbon double bond and wherein the structure:
##STR36## represents a "trans" isomer with respect to the methyl
moieties bonded to the carbon atoms making up the carbon-carbon
double bond and wherein the structure: ##STR37## represents a
stereo isomeric configuration wherein the carbon atoms having the
"*" are assymetric carbon atom in the molecule and wherein the
compound is a "trans isomer" with respect to the methyl moieties
bonded to the carbon atoms which make up the carbon-carbon double
bond.
The branched chain olefinic carbonates of our invention are
obtained by means by first reacting ketones produced according to
applications for United States Letters Patent Ser. No. 148,132
filed on Sept. 4, 1980 entitled: "BRANCHED KETONES, ORGANOLEPTIC
USES THEREOF AND PROCESS FOR PREPARING SAME" with a reducing agent
such as:
(a) one or more alkali metal borohydrides, e.g. sodium borohydride,
lithium borohydride and potassium borohydride;
(b) hydrogen, using a catalyst such as 5% palladium on carbon, 5%
palladium on calcium carbonate or palladium on barium sulfate (e.g.
"Lindlar Catalyst"); or
(c) lithium aluminum hydride;
(d) aluminum alkoxides, such as aluminum isopropyxide and aluminum
secondary epoxide,
according to the reaction: ##STR38## wherein R.sub.1 represents
methyl and then reacting the resulting alcohol with formic acid to
form the formate according to the reaction: ##STR39## and finally
reacting the resulting formate with dimethyl carbonate according to
the reaction: ##STR40## wherein in each of the molecules, one of
the dashed lines represents a carbon-carbon double bond and each of
the other of the dashed lines represent carbon-carbon single
bonds.
When carrying out the reaction for reacting the ketone having the
structure: ##STR41## with an alkali metal borohydride such as
sodium borohydride, the reaction is carried out in the presence of
a protic solvent which reacts relatively slowly or not at all with
the alkali metal borohydride when compared to the reaction of the
alkali metal borohydride with the ketone having the structure:
##STR42## Specific workable solvents which must "solvate" the
carbonyl moiety in order to enable the reaction to proceed at a
reasonable rate are isopropyl alcohol, n-propenol, n-butanol,
isobutyl alcohol and p-butyl alcohol.
The temperature of reaction is necessarily a function of:
(i) the yield desired;
(ii) the time of reaction;
(iii) the nature of the solvent used;
(iv) the pressure of the vapor over the reaction mass;
(v) the concentration of the reactant, the alkali metal borohydride
and the ketone having the structure: ##STR43## in the solvent; (vi)
the desired rate of reaction, and
(vii) the ratio of alkali metal borohydride:ketone having the
structure: ##STR44## It is preferred to carry out the reaction at
reflux conditions at atmospheric pressure. Thus, when using
isopropyl alcohol as a solvent where the mole ratio of alkali metal
borohydride:ketone having the structure: ##STR45## is 1:2, the
temperature of reaction is about 73.degree. C. and the time of
reaction is 3 hours. In the case of using an alkali metal
borohydride, the alcohol acts as a "solvent" and not as a
"reactant".
On the other hand, when using the aluminum alkoxide such as
aluminum secondary butoxide and aluminum isopropoxide, the solvent
must be a source of hydrogen which is the actual reducing agent in
the reaction. Thus, it is necessary that the "solvent" be a
"reactable solvent" such as isopropyl alcohol and not merely a
solvating solvent.
The mole ratio of alkali metal borohydride:ketone having the
structure: ##STR46## is preferably 1:2, which means that the
equivalent ratio regarding hydrogen:ketone is 2:1; that is, the
alkali metal borohydride is in 100% excess since theoretically only
one mole of the alkali metal borohydride is needed to react with 4
moles of ketone, since one mole of alkali metal borohydride
provides 4 atoms of hydrogen. interestingly and surprisingly in
this reaction and in all of the above reactions, the double bond
does get reduced during the reaction.
Insofar as the hydrogenation reaction is concerned with the ketone
having the structure: ##STR47## as the starting material or one of
the ketones defined according to the structure: ##STR48## as being
a starting material, the ketone is reacted with hydrogen in the
presence of a Raney Nickel catalyst or a palladium on carbon
catalyst or a "Lindlar" catalyst (palladium on calcium carbonate)
or palladium on barium sulfate. The percentage of palladium in the
palladium on carbon catalyst or in the palladium on calcium
carbonate catalyst or in the palladium on barium sulfate catalyst
varies from about 2% up to about 7% with a percentage of palladium
in the palladium on carbon catalyst or in the palladium on calcium
carbonate catalyst or in the palladium on barium sulfate catalyst
being preferred to be 5%. The temperature of reaction for the
hydrogenation may vary from about 10.degree. C. up to about
100.degree. C. with a preferred reaction temperature of 25.degree.
C.-35.degree. C. Since the reaction is exothermic, it is usually
necessary to provide external cooling to the reaction mass during
the course of the reaction. The pressure of hydrogen over the
reaction mass may vary from about 5 psig up to about 100 psig with
the most preferred pressure being 20 psig. Pressures greater than
150 psig will give rise to amounts of fully saturated alcohol. The
hydrogenation reaction may be carried out in the presence of or in
the absence of a solvent. When a solvent is used, it is required
that it be an inert (non-reactive) solvent such as isopropyl
alcohol, hexane or ethanol. If a solvent is used, it is preferred
that the mole ratio of solvent:ketone having the structure:
##STR49## be approximately 1:1. When a palladium containing
catalyst is used, the percentage of catalyst in the reaction mass
may vary from 0.125% up to about 2.0% with a percentage of catalyst
of about 0.25% being preferred. Where a Raney Nickel catalyst is
used, the percentage of catalyst in the reaction mass may vary from
about 3% up to about 10% with a percentage of catalyst of about 5%
being preferred.
If the reaction is carried out in the presence of the alkali metal
borohydride, the reaction mass is neutralized using weak acid and
the reaction product is then further washed with water and, if
necessary, sodium carbonate. In any event, the reaction mass is
ultimately distilled fractionally to yield the desired saturated
alcohol product having the generic structure: ##STR50## wherein
R.sub.1 is methyl or isopropyl and one of the dashed lines
represents a carbon-carbon double bond and the other of the dashed
lines represent carbon-carbon single bonds.
The reaction to form the formate ester is carried out by reacting
formic acid with the resulting alcohol in the presence of a
protonic acid catalyst such as 98% sulfuric acid or phosphoric
acid. The reaction preferably takes place at reflux conditions in
the presence of an inert solvent such as toluene or xylene. When
using toluene as a solvent and operating at atmospheric pressure,
the temperature of reaction, at reflux, is 92.degree.-98.degree. C.
The mole ratio of formic acid:alcohol is preferably in the range of
from 1 up to 1.5:1 with a mole ratio of formic acid:alcohol of
1:0.85 being preferred (based on 100% formic acid). Commercial
formic acid is 90% formic acid. At the end of the reaction, the
reaction mass is washed with water and the excess acid is
neutralized. The solvent is stripped off and the reaction product
is preferably used "as is" in the reaction of the formate with the
dimethyl carbonate.
The reaction of the resulting formate with dimethyl carbonate
according to the reaction: ##STR51## takes place in the presence of
an alkali metal alkoxide such as sodium methoxide, sodium ethoxide,
sodium t-butoxide, potassium methoxide, potassium ethoxide and
potassium t-butoxide. This reaction between the formate ester and
the dimethyl carbonate takes place in the absence of any additional
solvent. The mole ratio range of dimethyl carbonate:formate ester
may vary from 3 moles dimethyl carbonate:0.5 moles formate ester
down to 1 mole dimethyl carbonate:1 mole formate ester. It is
preferred that the mole ratio of dimethyl carbonate:formate ester
be about 2:1. The concentration in the reaction mass of alkali
metal alkoxide catalyst may vary from about 0.005 up to about 0.01
with a mole ratio of about 0.05 being preferred.
The reaction temperature range may vary from about 50.degree. C. up
to about 100.degree. C. and the reaction pressure may vary from
atmospheric pressure up to 10 atmospheres. Higher temperature of
reaction necessitates higher pressure over the reaction mass in
order to prevent the reaction product from evaporating
therefrom.
At the end of the reaction, the reaction product is purified
according to standard procedures such as fractional distillation
and, if necessary, chromatographic separation as by high pressure
liquid chromatography or GLC (vapor phase chromatography).
The branched chain olefinic methyl carbonates of our invention can
be used to contribute myrrh-like, labdanum-like aroma nuances to
perfume compositions, perfumed articles such as solid or liquid
cationic, nonionic, anionic or zwitterionic detergents, perfumed
polymers, fabric softener compositions, fabric softener articles,
optical brighteners, fabric conditioners, hair preparations,
shampoos and hair sprays. As olfactory agents, the branched chain
olefinic methyl carbonates of our invention can be formulated into
or used as components of a "perfume composition".
The term "perfume composition" is used herein to mean a mixture of
organic compounds including, for example, alcohols, aldehydes,
ketones, nitriles, ethers, lactones, esters other than the
carbonates of our invention, and frequently hydrocarbons which are
admixed so that the combined odors of the individual components
produce a pleasant or desired fragrance. Such perfume compositions
usually contain: (a) the main note or the "bouquet" or foundation
stone of the composition; (b) modifiers which round off and
accompany the main note; (c) fixatives which include odorous
substances which lend a particular note to the perfume throughout
all stages of evaporation and substances which retard evaporation
and (d) top notes which are usually low-boiling, fresh-smelling
materials.
In perfume compositions, the individual component will contribute
its particular olfactory characteristics, but the overall effect of
the perfume composition will be the sum of each of the effects of
each of the ingredients. Thus, the individual compounds of this
invention or mixtures thereof can be used to alter the aroma
characteristics of the perfume composition, for example, by
highlighting or moderating the olfactory reaction contributed by
another ingredient in the composition.
The amount of branched chain olefinic methyl carbonate of our
invention which will be effective in perfume compositions depends
upon many factors including the other ingredients, their amounts
and the effects which are desired. It has been found that perfume
compositions containing as little as 0.1% of the branched chain
olefinic methyl carbonates of our invention or even less and
perfume compositions containing as much as 70% of the branched
chain olefinic methyl carbonates of our invention can be used to
impart interesting myrrh-like, labdanum-like aroma nuances to
perfumed articles, perfume compositions and colognes. Such perfumed
articles include fabric softener compositions, drier-added fabric
softener articles, cosmetic powders, talc, solid or liquid anionic,
cationic, nonionic or zwitterionic detergents and perfumed
polymers. The amount employed can range up to 70% and will depend
on considerations of cost, nature of the end product and the effect
desired on the finished product and particular fragrance
sought.
Thus, the branched chain olefinic methyl carbonates of our
invention can be used alone or in a perfume composition as an
olfactory component, in solid or liquid anionic, cationic, nonionic
or zwitterionic detergents (including soaps), perfumed polymers
(those which are microporous and those which are macroporous and
contain particulate absorbent fillers such as talc or calcium
carbonate), space odorants and deodorants; perfumes, colognes,
toilet waters, bath salts, hair preparations such as lacquers,
brilliantines, pomades and shampoos; cosmetic preparations such as
creams, deodorants, hand lotions and sun screens; powders such as
talcs, dusting powders, face powders and the like.
When used as an olfactory component of a perfumed article such as a
microporous polymer or a macroporous polymer containing an
absorbent filler or such as a solid or liquid cationic, anionic,
nonionic or zwitterionic detergent or of a cosmetic powder, as
little as 0.01% of the branched chain olefinic methyl carbonates of
our invention will suffice to provide an interesting myrrh-like,
labdanum-like aroma. Generally no more than 0.8% of the branched
chain olefinic methyl carbonates of our invention are required in
the perfumed article.
In addition, the perfume compositions of our invention can contain
a vehicle or carrier for the branched chain olefinic methyl
carbonates of our invention, alone, or with other ingredients. The
vehicle can be a liquid such as an alcohol such as ethanol, a
glycol such as propylene glycol or the like. The carrier can be an
absorbent solid such as a gum (e.g. xanthan gum, gum arabic or guar
gum) or components for encapsulating the composition as by
coacervation (using gelatin) or as by shell polymerization around
the liquid fragrance center using a urea formaldehyde
prepolymer.
The following Examples A, I, II, III and IV set forth processes
required to prepare the branched chain olefinic methyl carbonates
of our invention. The examples following Example IV, Examples V et
seq. represent methods for using the branched chain olefinic methyl
carbonates of our invention for their organoleptic properties.
Unless otherwise indicated, all parts and percentages are by
weight.
EXAMPLE A
Preparation of Diisoamylene ##STR52##
Diisoamylene is prepared according to one of the procedures set
forth in the following references:
(i) Murphy & Lane, Ind. Eng. Chem., Prod. Res. Dev., Vol. 14,
No. 3, 1975 p. 167 (Title: Oligomerization of 2-Methyl-2-Butene in
Sulfuric Acid and Sulfuric-Phosphoric Acid Mixtures).
(ii) Whitmore & Mosher, Vol. 68, J. Am. Chem. Soc., February,
1946, p . 281 (Title: The Depolymerization of
3,4,5,5-Tetramethyl-2-hexene and 3,5,5-Trimethyl-2-heptene in
Relation to the Dimerization of Isoamylenes).
(iii) Whitmore & Stahly, Vol. 67, J. Am. Chem. Soc., December,
1945; p. 2158 (Title: The Polymerization of Olefins. VIII The
Polymerization of Olefins in Relation to Intramolecular
Rearrangements. II).
(iv) U.S. Pat. No. 3,627,700 issued on Dec. 14, 1971, (Zuech).
(v) U.S. Pat. No. 3,538,181 issued on Nov. 3, 1970, (Banks).
(vi) U.S. Pat. No. 3,461,184 issued on Aug. 12, 1969 (Hay, et
al).
(vii) Gurwitsch, Chemische Berichte, 1912, Vol. 2, p. 796
(Production of Di-isoamylene From Isoamylene Using Mercury Acetate
Catalyst).
As an illustration, and not by way of limitation, the following
example sets forth the preparation of diisoamylenes useful in
producing the fragrance materials of our invention.
Over a period of ten hours, 2-methyl-2-butene is pumped through a
5'.times.5/8 (0.625 inch) tube packed with 15.0 grams of
polystyrene sulfonic acid catalyst at a temperature of 100.degree.
C. and at a pressure of 400 psig.
The resulting material was distilled in a fractionation column in
order to separate the diisoamylene from the higher molecular weight
polymers, which are formed during the reaction as by-products. This
material distills at 36.degree.-40.degree. C. vapor temperature;
74.degree.-94.degree. C. liquid temperature and 4-5 mm/Hg
pressure.
FIG. AA represents the GLC profile for the reaction product of this
Example A using a 70% sulfuric acid catalyst at 35.degree. C.
FIG. AB represents the GLC profile for the reaction product of this
Example A using an Amberlyst.RTM. 15 acidic ion exchange resin
catalyst at a temperature of 150.degree. C.
FIG. AC represents the GLC profile for the reaction product of this
Example A, using an Amberlyst.RTM. 15 catalyst at 100.degree.
C.
FIG. AD represents the GLC profile for the reaction product of this
Example A, using a sulfuric acid catalyst and an
alpha-methylstyrene diluent at 35.degree. C. according to the
conditions of United Kingdom Patent Specification 796,130 (crude
reaction product).
FIG. AE represents the GLC profile for the reaction product of this
Example A, using a sulfuric acid catalyst at 35.degree. C. and an
alpha-methylstyrene diluent according to the conditions of United
Kingdom Patent Specification No. 796,130 (distilled reaction
product). Distillation range: 36.degree.-40.degree. C. vapor
temperature; 74.degree.-94.degree. C. liquid temperature and 4-5
mm/Hg pressure.
FIG. BA represents the NMR spectrum for peak 301 of the GLC profile
of FIG. AE. Peak 301 has been determined by analysis to be the
compound having the structure: ##STR53##
FIG. BB represents the infra-red spectrum for peak 301 of the GLC
profile of FIG. AE.
FIG. CA represents the NMR spectrum for peak 302 of the GLC profile
of FIG. AE. Peak 302 contains the compounds having the structures:
##STR54##
FIG. CB represents the infra-red spectrum for peak 302 of the GLC
profile of FIG. AE.
FIG. D represents the NMR spectrum for peak 302 of the GLC profile
of FIG. AB.
EXAMPLE I
Preparation of Acetyl Derivative of Diisoamylene ##STR55## wherein
in each of the structures containing dashed lines, these structures
represent mixtures of molecules wherein in each of the molecules,
one of the dashed lines respresents a carbon-carbon double bond and
each of the other of the dashed lines respresent carbon-carbon
single bonds.
Into a 2-liter reaction flask equipped with stirrer, thermometer,
reflex condenser and heating mantle, is placed 1000 g of acetic
anhydride and 80 g of boron trifluoride diethyl etherate. The
resulting mixture is heated to 80.degree. C. and, over a period of
40 minutes, 690 g of diisoamylene prepared according to the
illustration in Example A, supra, (distilling at
36.degree.-40.degree. C. vapor temperature; 74.degree.-94.degree.
C. liquid temperature and 4-5 mm/Hg pressure) is added.
The reaction mass is maintained at 82.degree.-85.degree. C. for a
period of 5.5 hours, whereupon it is cooled to room temperature.
The reaction mass is then added to one liter of water and the
resulting mixture is stirred thereby yielding two phases; an
organic phase and an aqueous phase. The organic phase is separated
from the aqueous phase and neutralized with two liters of 12.5%
sodium hydroxide followed by one liter of saturated sodium chloride
solution. The resulting organic phase is then dried over anhydrous
sodium sulfate and distilled in a one plate distillation column,
yielding the following fractions:
______________________________________ Vapor Liquid Weight of
Fraction Temp. Temp. mm/Hg Fraction No. (.degree.C.) (.degree.C.)
Pressure (g.) ______________________________________ 1 33/68 62/77
8/8 161 2 69 79 4 100 3 72 86 3.0 191 4 88 134 3.0 189
______________________________________
The resulting material is then distilled on a multi-plate
fractionation column, yielding the following fractions at the
following reflux ratios:
______________________________________ Vapor Liquid Reflux Weight
of Fraction Temp. Temp. mm/Hg Ratio Fraction No. (.degree.C.)
(.degree.C.) Pressure R/D (g.)
______________________________________ 1 30/65 62/83 5/5 9:1 30.8 2
68 84 5 9:1 52.8 3 68 85 5 9:1 34 4 69 87 5 9:1 43 5 69 87 5 9:1 34
6 71 88 4 4:1 41 ______________________________________
______________________________________ Vapor Liquid Reflux Weight
of Fraction Temp. Temp. mm/Hg Ratio Fraction No. (.degree.C.)
(.degree.C.) Pressure R/D (g.)
______________________________________ 7 70 88 5 4:1 36.5 8 71 91 5
4:1 42 9 73 95 3 4:1 42.5 10 80 106 3 4:1 39 11 80 142 3 4:1 50.8
12 80 220 3 4:1 24 ______________________________________
GLC, NMR, IR and mass spectral analyses yield the information that
the resulting material is a mixture of cis and trans isomers having
a generic structure: ##STR56## wherein in each of the molecules,
one of the dashed lines is a carbon-carbon double bond and the
other of the dashed lines is a carbon-carbon single bond and,
primarily, this mixture contains the molecular species (cis and
trans isomers) as follows: ##STR57##
Fractions 2-12 are bulked for use in the following reaction in
Examples II(A) and II(B).
FIG. 1 sets forth the GLC profile for the reaction product of
Example I, containing compounds defined according to the structure:
##STR58## wherein in each molecule of the mixture, one of the
dashed lines is a carbon-carbon double bond and the other of the
dashed lines are carbon-carbon single bonds.
FIG. 2A represents the infra-red spectrum of Peak 3 of the GLC
profile of FIG. 1.
FIG. 2B represents the infra-red spectrum of Peak 4 of the GLC
profile of FIG. 1.
FIG. 2C represents the infra-red spectrum for Peak 5 of the GLC
profile of FIG. 1.
FIG. 2D represents the infra-red spectrum for Peak 7 of the GLC
profile of FIG. 1.
FIG. 2E represents the infra-red spectrum for Peak 7 of the GLC
profile of FIG. 1.
FIG. 2F represents the infra-red spectrum for Peak 8 of the GLC
profile of FIG. 1.
FIG. 2G represents the infra-red spectrum for Peak 9 of the GLC
profile of FIG. 1.
FIG. 2H represents the infra-red spectrum for Peak 10 of the GLC
profile of FIG. 1.
FIG. 2J represents the NMR spectrum for a mixture of compounds
having the structures: ##STR59## produced according to Example
I.
FIG. 2K represents the NMR spectrum for the compound having the
structure: ##STR60## produced according to Example I.
FIG. 2L represents the NMR spectrum for the compound containing the
structure: ##STR61## produced according to Example I.
EXAMPLE II
Preparation of Acetyl Derivative of Diisoamylene ##STR62##
EXAMPLE II(A)
Into a 5-liter reaction flask equipped with electric stirrer,
thermometer, addition funnel, 24/42 y-tube, condenser, heating
mantle and nitrogen purge accessories are added 41 ml of 70%
methane sulfonic acid followed by 30 grams of phosphorous
pentoxide. The resulting mixture exotherms to 60.degree. C.
Over a period of 7 minutes, 235 ml of acetic anhydride is added to
the reaction mass while maintaining same at a temperature of
65.degree. C. Over a period of 30 minutes while maintaining the
reaction temperature at 80.degree. C., 516 ml of diisoamylene
prepared according to the illustration of Example A is added
dropwise to the reaction mass. At the end of the addition of the
diisoamylene, GLC analysis indicates 42% product.
The reaction mass is added to a 5 gallon open head separatory flask
containing 1 liter of water.
The resulting mixture is washed with 1 liter of 12% sodium
hydroxide followed by 1 liter of saturated sodium chloride
solution. 100 ml toluene is added to help separation.
GLC, NMR, IR and mass spectral analyses yield the information that
the resulting organic phase is a mixture of compounds defined
according to the generic structure: ##STR63## wherein in each of
the molecules one of the dashed lines is a carbon-carbon double
bond and the other two of the dashed lines represent carbon-carbon
single bonds.
The resulting reaction product is then dried over anhydrous
magnesium sulfate and distilled on a 3-inch stone column yielding
the following fractions:
______________________________________ Vapor Liquid Fraction Temp.
Temp. mm/Hg No. (.degree.C.) (.degree.C.) Pressure
______________________________________ 1 65/65 103/92 113/35 2 60
80 1 3 52 89 1 4 61 134 1 5 73 140 1
______________________________________
Fractions 2, 3 and 4 are bulked and are used in the syntheses in
subsequent examples.
FIG. 3 represents the GLC profile for the reaction product of
Example II(A) containing the structures defined according to the
genus having the structure: ##STR64## wherein in each of the
molecules of the mixture, one of the dashed lines represents a
carbon-carbon double bond and each of the other of the dashed lines
represent carbon-carbon single bonds.
EXAMPLE II(B)
To a 500 ml reaction flask equipped with reflux condenser, addition
funnel, thermometer, Thermowatch, heating mantle, cooling bath and
nitrogne purge accessories, is added 406 ml of acetic anhydride and
30 ml boron trifluoride etherate. The reaction mass is heated to
60.degree. C. and while maintaining the reaction mass at 60.degree.
over a period of 30 minutes, diisoamylene, prepared according to
the illustration of Example A is added. The resulting reaction mass
is then heated, with stirring at 60.degree. C. for a period of 12
hours. At the end of the 12 hour period, the reaction mass is
distilled yielding the following fractions:
______________________________________ Vapor Liquid Weight of
Fraction Temp. Temp. mm/Hg Fraction No. (.degree.C.) (.degree.C.)
pressure (g.) ______________________________________ 1 50/58 60/70
2.5 330 2 67 87 1.4 329 3 71 88 3.0 65 4 90 115 3.0 195
______________________________________
Fractions 2, 3 and 4 are bulked for use in subsequent examples.
The resulting mass, by GLC, IR, NMR and mass spectral analyses
consist of compounds defined according to the generic structure:
##STR65## wherein in each of the molecules one of the dashed lines
is a carbon-carbon double bond and the other two of the dashed
lines represent carbon-carbon single bonds.
FIG. 4 sets forth the GLC profile for the reaction product of this
Example II(B).
EXAMPLE III
Preparation of Diisoamylene Methyl Carbinol ##STR66##
Into a 2 liter reaction flask equipped with reflux condenser,
addition funnel, thermometer, heating mantle, and nitrogen bleed is
placed 1 liter of isopropyl alcohol followed by 38 grams of sodium
borohydride. The resulting mixture is heated to reflux and over a
period of 40 minutes while maintaining the reflux temperature at
48.degree. C. dropwise addition of acetyl diisoamylene according to
Example I (368 grams) (bulked fractions 2-12 of the distillation)
is carried out.
At the end of the addition of the 368 grams of acetyl diisoamylene,
the reaction mass is stirred at a temperature of 73.degree. C. for
a period of 3 hours. The reaction mass is then transferred to a
separatory flask containing 1 liter of water. 200 ml 5%
hydrochloric acid is added to the separatory funnel and the organic
layer is separated from the inorganic layer.
The organic layer is washed with one liter of sodium carbonate and
is then distilled on a 1" packed stone column yielding the
following fractions:
______________________________________ Vapor Liquid Fraction Temp.
Temp. Pressure Number (.degree.C.) (.degree.C.) mm/Hg
______________________________________ 1 25/20 18/20 10 2 80 90 .2
3 81 92 .2 4 83 96 .2 5 81 130 .2 6 80 200 .2
______________________________________
Fractions 2-4 are bulked for use in the synthesis in subsequent
examples.
The resulting product (bulked fractions 2-4) is analyzed by GLC,
NMR and IR analysis to contain a mixture of compounds defined
according to the structure: ##STR67## wherein in each of the
compounds one of the dashed lines represents a carbon-carbon double
bond and each of the other of the dashed lines represent
carbon-carbon single bonds.
FIG. 5 is the GLC profile of the reaction product (conditions:
6'.times.1/4" SF 96 column programmed at 100.degree.-120.degree. C.
at 8.degree. C. per minute).
FIG. 6 is the infra red spectrum for the distillation product,
bulked fractions 2-4.
EXAMPLE IV
Preparation of the Methyl Carbonate of Diisoamylene Methyl Carbinol
##STR68##
EXAMPLE IV(A)
Into a 1 liter reaction flask equipped with nitrogen blanket
apparatus and Bidwell trap, and reflux condenser, stirrer and
thermometer is placed 159 grams of diisoamylene methyl carbinol
produced according to Example III (bulked fractions 2-4) (0.85
moles); 55.2 grams of 90% formic acid (1.1 moles); 1 ml of 98%
sulfuric acid and 250 ml toluene.
The reaction mass is heated to reflux (92.degree.-97.degree. C.)
and maintained at a temperature in the range of
92.degree.-97.degree. C. for a period of 2 hours. At the end of the
2 hour period, the reaction mass is washed with the following
materials:
(i) 500 ml water;
(ii) 500 ml water;
(iii) 500 ml saturated sodium chloride;
(iv) 500 ml saturated sodium chloride.
The solvent is stripped from the reaction mass on a rotary
evaporator and GLC, NMR, IR and mass spectral analyses indicate
that the yield is 54%.
The resulting product is then used in the procedure of Example
IV(B).
EXAMPLE IV(B)
Into a 1 liter reaction flask equipped with thermometer, reflux
condenser, heating mantle, Bidwell trap and nitrogen blanket
apparatus is placed a mixture of 5 grams of sodium methoxide and 97
grams (1.04 moles) of dimethyl carbonate. 20 ml of the formate
ester prepared in Example IV(A), supra, is then added to the
mixture and the mixture is heated to 80.degree. C. While
maintaining the reaction mass at 78.degree.-80.degree. C., the
remaining formate ester (total: 208 grams; 0.52 moles) is added.
The reaction mass is then heated at a temperature in the range of
88.degree.-104.degree. C. over a period of 4 hours.
At the end of the reaction, the reaction mass is transferred to a
separatory funnel and is washed with 2 one-liter portions of water
followed by 0.5 liters of saturated sodium chloride. The reaction
mass is then distilled on a 6" stone packed column yielding the
following fractions:
______________________________________ Vapor Liquid Weight of
Fraction Temp. Temp. Pressure Fraction Number (.degree.C.)
(.degree.C.) mm/Hg. (grams) ______________________________________
1 43/58 79/89 4/2.1 40 2 75 97 3.2 22 3 87 101 3.2 25 4 88 103 3.2
18 5 90 113 3.2 22 6 83 160 3.2 29
______________________________________
FIG. 8 is the GLC profile for fraction 5 of the foregoing
distillation (conditions: 12% SF-96 6'.times.1/4" column programmed
at 100.degree.-220.degree. C. at 8.degree. C. per minute).
FIG. 9 is the NMR spectrum for fraction 5 of the foregoing
distillation.
FIG. 10 is the infra-red spectrum for fraction 5 of the foregoing
distillation.
Fraction 5 has an excellent myrrh, labdanum aroma profile.
EXAMPLE V
Chypre Perfume Base
The following chypre perfume formulation is prepared:
______________________________________ Ingredients Parts by Weight
______________________________________ Sandalwood oil (Haiti) 220
Bergamot oil 227 Rose absolute 50 Oil of coriander 25 Methyl
jasmonate 50 Patchouli oil 40 Red thyme oil 7 Vetiver oil Bourbon
110 Diisoamylene methyl carbinol methyl carbonate prepared
according to Example IV(B), fraction 5 of distillation 55 Oakmoss
absolute 110 Castorium resinoid 70 Neroli oil 20 Isosafrole 1 Musk
ambrette 15 Civetone 5 ______________________________________
The use of the carbonate produced according to Example IV(B)
imparts an excellent labdanum topnote with myrrh-like undertone to
this chypre base formulation.
EXAMPLE VI
Opoponax Perfume Formulation
The following perfume formulation is prepared:
______________________________________ Ingredients Parts by Weight
______________________________________ Bergamot oil 300 Orris oil
50 Opoponax resinoid 50 Lemon oil 20 Jasmin natural 50 Bulgarian
rose oil 80 Ginger oil 10 Diisoamylene methyl carbinol methyl
carbonate prepared according to Example IV(B) 150 Galbanum resin 40
Vetiver oil 25 Violet essence 50 Costus oil 50
2,3,8,8-tetramethyl-2-acetyl- delta 9,10-octahydro naphthalene 200
______________________________________
The use of the carbonate prepared according to Example IV(B),
fraction 5, imparts to this apoponax perfume formulation an
excellent myrrh undertone with labdanum-like topnotes.
The carbonate ester of Example IV(B) can be used to replace the
myrrh resinoid necessary for this opoponax formulation. Indeed, an
improvement occurs when the carbonate ester is used in place of the
myrrh resinoid formulation as a result of the labdanum-like nuances
imparted.
EXAMPLE VII
Preparation of Cosmetic Powder Compositions
Cosmetic powder compositions are prepared by mixing in a ball mill
100 grams of talcum powder with 0.25 grams of each of the
substances set forth in Table I below. Each of the cosmetic powder
compositions has an excellent aroma as described in Table I
below.
TABLE I ______________________________________ Substance Aroma
Description ______________________________________ Diisoamylene
methyl carbinol A myrrh, labdanum aroma methyl carbonate prepared
with high intensity and according to Example IV(B), long lasting
power. fraction 5 Fragrance formulation of A chypre like essence
Example V with labdanum topnotes and myrrh-like undertones.
Fragrance formulation of An opoponax aroma with Example VI myrrh
undertones and pleasant labdanum-like topnotes.
______________________________________
EXAMPLE VIII
Perfumed Liquid Detergents
Concentrated liquid detergents (lysine salt of n-dodecylbenzene
sulfonic acid as more specifically described in U.S. Pat. No.
3,948,818, issued on Apr. 6, 1976 incorporated by reference herein)
with aroma nuances as set forth in Table I of Example VII, are
prepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and 0.35% of
the substance set forth in Table I of Example VII. They are
prepared by adding and homogeneously mixing the appropriate
quantity of substance set forth in Table I of Example VII in the
liquid detergent. The detergents all possess excellent aromas as
set forth in Table I of Example VII, the intensity increasing with
greater concentrations of substance as set forth in Table I of
Example VII.
EXAMPLE IX
Preparation of Colognes and Handkerchief Perfumes
Compositions as set forth in Table I of Example VII are
incorporated into colognes at concentrations of 2.0%, 2.5%, 3.0%,
3.5%, 4.0%, 4.5% and 5.0% in 80%, 85%, 90% and 95% aqueous food
grade ethanol solutions; and into handkerchief perfumes at
concentrations of 15%, 20%, 25% and 30% (in 80%, 85%, 90% and 95%
aqueous food grade ethanol solutions). Distinctive and definitive
fragrances as set forth in Table I of Example VII are imparted to
the colognes and to the handkerchief perfumes at all levels
indicated.
EXAMPLE X
Preparation of Soap Compositions
One hundred grams of soap chips [per sample] (IVORY.RTM., produced
by the Procter & Gamble Company of Cincinnati, Ohio), are each
mixed with one gram samples of substances as set forth in Table I
of Example VII until homogeneous compositions are obtained. In each
of the cases, the homogeneous compositions are heated under 8
atmospheres pressure at 180.degree. C. for a period of three hours
and the resulting liquids are placed into soap molds. The resulting
soap cakes, on cooling, manifest aromas as set forth in Table I of
Example VII.
EXAMPLE XI
Preparation of Solid Detergent Compositions
Detergents are prepared using the following ingredients according
to Example I of Canadian Pat. No. 1,007,948 (incorporated by
reference herein):
______________________________________ Ingredient Percent by Weight
______________________________________ "Neodol.RTM. 45-11" (a
C.sub.14 -C.sub.15 alcohol ethoxylanted with 11 moles of ethylene
oxide) 12 Sodium carbonate 55 Sodium citrate 20 Sodium sulfate,
water q.s. brighteners ______________________________________
This detergent is a phosphate-free detergent. Samples of 100 grams
each of this detergent are admixed with 0.10, 0.15, 0.20 and 0.25
grams of each of the substances as set forth in Table I of Example
VII. Each of the detergent samples has an excellent aroma as
indicated in Table I of Example VII.
EXAMPLE XII
Utilizing the procedure of Example I at column 15 of U.S. Pat. No.
3,632,396 (the disclosure of which is incorporated herein by
reference), nonwoven cloth substrates useful as drier-added fabric
softening articles of manufacture are prepared wherein the
substrate, the substrate coating, the outer coating and the
perfuming material are as follows:
1. A water "dissolvable" paper ("Dissolvo Paper")
2. Adogen 448 (m.p. about 140.degree. F.) as the substrate coating;
and
3. An outer coating having the following formulation (m.p. about
150.degree. F.):
57% C.sub.20-22 HAPS
22% isopropyl alcohol
20% antistatic agent
1% of one of the substances as set forth in Table I of Example
VII
Fabric softening compositions prepared according to Example I at
column 15 of U.S. Pat. No. 3,632,396 having aroma characteristics
as set forth in Table I of Example VII, supra, consist of a
substrate coating having a weight of about 3 grams per 100 square
inches of substrate; a first coating located directly on the
substrate coating consisting of about 1.85 grams per 100 square
inches of substrate; and an outer coating coated on the first
coating consisting of about 1.4 grams per 100 square inches of
substrate. One of the substances of Table I of Example VII is
admixed in each case with the outer coating mixture, thereby
providing a total aromatized outer coating weight ratio to
substrate of about 0.5:1 by weight of the substrate. The aroma
characteristics are imparted in a pleasant manner to the head space
in a drier on operation thereof in each case using said drier-added
fabric softener non-woven fabrics and these aroma characteristics
are described in Table I of Example VII, supra.
EXAMPLE XIII
Hair Spray Formulations
The following hair spray formulation is prepared by first
dissolving PVP/VA E-735 copolymer manufactured by the GAF
Corporation of 140 West 51st Street, New York, N.Y., in 91.62 grams
of 95% food grade ethanol. 8.0 grams of the polymer is dissolved in
the alcohol. The following ingredients are added to the PVP/VA
alcoholic solution:
______________________________________ Dioctyl sebacate 0.05 weight
percent Benzyl alcohol 0.10 weight percent Dow Corning 473 fluid
(prepared by the Dow Corning 0.10 weight percent Corporation) Tween
20 surfactant (prepared by ICI America 0.03 weight percent
Corporation) One of the perfumery sub- stances as set forth in
Table I of Example VII 0.10 weight percent
______________________________________
The perfuming substances as set forth in Table I of Example VII add
aroma characteristics as set forth in Table I of Example VII which
are rather intense and aesthetically pleasing to the users of the
soft-feel, good-hold pump hair sprays.
EXAMPLE XIV
Conditioning Shampoos
Monamid CMA (prepared by the Mona Industries Company) (3.0 weight
percent) is melted with 2.0 weight percent coconut fatty acid
(prepared by Procter & Gamble Company of Cincinnati, Ohio); 1.0
weight percent ethylene glycol distearate (prepared by the Armak
Corporation) and triethanolamine (a product of Union Carbide
Corporation) (1.4 weight percent). The resulting melt is admixed
with Stepanol WAT produced by the Stepan Chemical Company (35.0
weight percent). The resulting mixture is heated to 60.degree. C.
and mixed until a clear solution is obtained (at 60.degree. C.).
This material is "COMPOSITION A".
Gafquat.RTM. 755 N polymer (manufactured by GAF Corporation of 140
West 51st Street, New York, N.Y.) (5.0 weight percent) is admixed
with 0.1 weight percent sodium sulfite and 1.4 weight percent
polyethylene glycol 6000 distearate produced by Armak Corporation.
This material is "COMPOSITION B".
The resulting COMPOSITION A & COMPOSITION B are then mixed in a
50:50 wt ratio of A:B and cooled to 45.degree. C. and 0.3 wt
percent of perfuming substance as set forth in Table I of Example
VII is added to the mixture. The resulting mixture is cooled to
40.degree. C. and blending is carried out for an additional one
hour in each case. At the end of this blending period, the
resulting material has a pleasant fragrance as indicated in Table I
of Example VII.
EXAMPLE XV
A fabric conditioner produced according to the method of U.S. Pat.
No. 4,291,072 issued on Sept. 22, 1981 is produced whereby the
sheet consisting of non-woven rayon substrate as set forth at
column 3, lines 25-34 passed through the bath of molten cationic
fabric softener-isopropenyl mixture is passed through the bath at
10 atmospheres pressure, during which time a fragrance material as
set forth in Table I of Example VII is added at the rate of 0.35%.
The resulting sheet when used with a clothing batch gives rise to a
pleasant aroma in the head space above the clothing batch as set
forth in Table I of Example VII.
* * * * *